Organic additive-copper(II) complexes as plating precursors

Cu(II) ions previously coordinated with typical electroplating organic additives were investigated as an alternative source of metal for plating bath. The coordination complexes were isolated from reaction between CuSO(4) and organic additives as ligands (oxalate ion, ethylenediamine or imidazole). Deposits over 1010 steel were successfully obtained from electroplated baths using the complexes without any addition of free additives, at pH = 4.5 (H(2)SO(4)/Na(2)SO(4)). These deposits showed better morphologies than deposits obtained from CuSO(4) solution either in the absence or presence of oxalate ion as additive (40 mmol L(-1)), at pH = 4.5 (H(2)SO(4)/Na(2)SO(4))It is suggestive that the starting metal plating coordinated with additives influences the electrode position processes, providing deposits with corrosion potentials shifted over + 200 mV in 0.5 mol L(-1) NaCl (1 mV s(-1)). The resistance against corrosion is sensitive to the type of additive-complex used as precursor. The complex with ethylenediamine presented the best deposit results with the lowest pitting potential (-0.27 V vs 3.0 mol L(-1) CE). It was concluded that the addition of free additives to the electrodeposition baths is not necessary when working with previously coordinated additives. Thus, the complexes generated in ex-situ are good alternatives as plating precursors for electrodeposition bath. (C) 2009 Elsevier B.V. All rights reserved.

A novel nanostructured composite formed by interaction of copper octa(3-aminopropyl)octasilsesquioxane with azide ligands: Preparation, characterization and a voltammetric application

This study presents the preparation, characterization and application of copper octa(3-aminopropyl)octasilsesquioxane following its subsequent reaction with azide ions (ASCA). The precursor (AC) and the novel compound (ASCA) were characterized by Fourier transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), scanning electronic microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analyses and voltammetric technique. The cyclic voltammogram of the modified graphite paste electrode with ASCA (GPE-ASCA), showed one redox couple with formal potential (E(1/2)(ox)) = 0.30 V and an irreversible process at 1.1 V (vs. Ag/AgCl; NaCl 1.0 M; v = 20 mV s(-1)). The material is very sensitive to nitrite concentrations. The modified graphite paste electrode (GPE-ASCA) gives a linear range from 1.0 x 10(-4) to 4.0 x 10(-3) mol L(-1) for the determination of nitrite, with a detection limit of 2.1 x 10(-4) mol L(-1) and the amperometric sensitivity of 8.04 mA/mol L(-1). (C) 2010 Elsevier Ltd. All rights reserved.

Factors influencing tourism sustainability : The case of the World Heritage Falun Great Copper Mountain

This thesis focuses on identifying hindrances of achieving a sustainable tourism development on a base of a World Heritage Site. Using a case study of the World Heritage Site Falun Great Copper Mountain, the thesis assesses the situational context by using qualitative methods. Five semi- structured interviews with influential stakeholders were conducted to get an inside view of the current situation and to identify site-specific issues. The thesis identifies a number of factors that determine the successful implementation of measures leading towards sustainable tourism in the long-run; the most important being the lack of clear guidelines for the whole destination and no holistic planning approach within the municipality. The thesis concludes that despite the increased pressures towards establishment of sustainable tourism, the concept remains challenging to operationalize for the World Heritage Site without frameworks and tools from UNESCO.

Replacing Finned Copper withCorrugated Stainless Steel, forthe Heat Exchangers of a SolarCombisystem Store : Performance and EconomicEvaluation

The importance of investigating cost reduction in materials and components for solar thermal systems is crucial at the present time. This work focuses on the influence of two different heat exchangers on the performance of a solar thermal system. Both heat exchangers studied are immersed helically coiled, one made with corrugated stainless steel tube, and the other made with finned copper tube with smooth inner surface.A test apparatus has been designed and a simple test procedure applied in order to study heat transfer characteristics and pressure drop of both coils. Thereafter, the resulting experimental data was used to perform a parameter identification of the heat exchangers, in order to obtain a TRNSYS model with its corresponding numerical expression. Also a representative small-scale combisystem model was designed in TRNSYS, in order to study the influence of both heat exchangers on the solar fraction of the system, when working at different flow rates.It has been found that the highest solar fraction is given by the corrugated stainless steel coil, when it works at the lowest flow rate (100 l/hr). For any higher flow rate, the studied copper coil presents a higher solar fraction. The advantageous low flow performance of stainless steel heat exchanger turns out to be beneficial for the particular case of solar thermal systems, where it is well known that low flow collector loops lead to enhanced store stratification, and consequently higher solar fractions.Finally, an optimization of the stainless steel heat exchanger length is carried out, according to economic figures. For the given combisystem model and boundary conditions, the optimum length value is found between 10 and 12 m.

Monitoramento morfológico do xerogel híbrido 3-(1,4-fenilenodiamina)propil/silica obtido sob diferentes condições de síntese

Neste trabalho, foi obtido o xerogel híbrido 3-(1,4-fenilenodiamina) propil/sílica, usando-se o método sol-gel de síntese, variando-se as condições experimentais de síntese. Foram usados como reagentes precursores o tetraetilortosilicato (TEOS) e o 3-[(1,4-fenilenodiamina)propil]trimetoxisilano (FDAPS) sintetizado em nosso laboratório. As condições experimentais de síntese variadas foram: a concentração de precursor orgânico (FDAPS), a temperatura de gelificação, o tipo de solvente e o pH do meio reacional. O trabalho foi dividido em duas etapas: na primeira, foram obtidas duas séries de materiais onde se variou a temperatura de gelificação (5, 25, 50 e 70 °C), além da quantidade de precursor orgânico (FDAPS), adicionado à síntese (1,5 e 5,0 mmol). Na segunda etapa variou-se o pH do meio reacional (4, 7 e 10) além do tipo de solvente (etanol, butanol e octanol), mantendo-se a quantidade de precursor orgânico adicionado e a temperatura de gelificação constantes em 5,0 mmol e 25 oC, respectivamente. Em ambas etapas utilizou-se HF como catalisador e manteve-se o sistema fechado, porém não vedado, durante a gelificação. Na caracterização dos xerogéis híbridos foram usadas as seguintes técnicas: a) termoanálise no infravermelho, para estimar a estabilidade térmica do componente orgânico além da fração de orgânicos dispersos na superfície; b) isotermas de adsorção e dessorção de nitrogênio, para determinação da área superficial específica, do volume e da distribuição de tamanho de poros; c) análise elementar para estimar a fração de componente orgânico presente no xerogel e d) microscopia eletrônica de varredura onde foi possível observar textura, compactação e presença de partículas primárias nos xerogéis. A partir dos resultados de caracterização foi possível avaliar a influência dos parâmetros experimentais de síntese nas características dos xerogéis híbridos obtidos. Xerogéis híbridos com maior teor de orgânicos foram mais influenciados pela variação da temperatura de gelificação. Um aumento na temperatura de gelificação produz xerogéis com menor porosidade, entretanto, com maior estabilidade térmica do componente orgânico. Considerando-se estabilidade térmica e porosidade, as amostras gelificadas a 25 oC apresentaram os melhores resultados. Em relação à variação de pH e solvente, as amostras gelificadas em pH ácido foram as que apresentaram maior porosidade, enquanto que a maior estabilidade térmica foi alcançada usando-se etanol como solvente.

Contribuição ao estudo da argamassa com adição de silica ativa em reforços de elementos comprimidos de concreto

VASKE, N.R. Contribuição ao Estudo da Argamassa com Adição de Sílica Ativa em Reforços de Elementos Comprimidos de Concreto. 2004. Dissertação (Mestrado em Engenharia) – Programa de Pós-Graduação em Engenharia Civil, UFRGS, Porto Alegre. No uso de argamassa com adição de sílica ativa como material de reforço, adotam-se valores de resistência à compressão provenientes de ensaios normatizados, cujos valores não são representativos da técnica adotada. Na execução de um reforço, cada porção de argamassa que é lançada sofre um adensamento que varia em função da energia com que colide com o substrato, gerando, desta forma, pontos de diferentes resistências por toda a extensão do reforço, refletindo diretamente sobre a resistência do reforço como um todo, que por sua vez define a nova capacidade de carga do elemento estrutural em questão. Procurando verificar o comportamento “in loco” da argamassa de reforço, executou-se uma placa de argamassa com adição de sílica ativa com dimensões iguais a um reforço de uma das faces de um pilar, sendo extraídas amostras prismáticas desta placa e ensaiadas à compressão e determinada uma resistência média que, comparada com a resistência média obtida de corpos-de-prova cilíndricos, moldados com a mesma argamassa com que foi executada a placa demonstrou que a resistência média à compressão das amostras prismáticas extraídas da placa apresenta, particularmente neste estudo, uma redução em relação à resistência média à compressão resultante dos corpos-de-prova cilíndricos da ordem de 35%. Em seqüência foram moldados seis pilares de concreto, sendo três reforçados com argamassa com adição de sílica ativa e os outros três como testemunhos. Após a ruptura dos pilares foram analisados os resultados teóricos e resultados experimentais das cargas de ruptura, aderência entre o substrato e a argamassa de reforço e a redução de resistência à compressão observada nos ensaios preliminares da argamassa. Pelas análises realizadas verificou-se a eficiência da técnica de reforço quanto ao aumento da capacidade de carga, da ordem de 72 %, aderência adequada entre o substrato e a argamassa de reforço e confirmação da redução da resistência à compressão da argamassa nos níveis propostos.

Mutagênese induzida por flavonóides presentes do decocto das cascas da aroeira (Schinus terebinthifolius, Raddi)

The decoction of Brazilian pepper tree barks (Schinus terebinthifolius, Raddi), is used in medicine as wound healing and antiinflamatory. Once extracts from this plant are used for acceleration of scar s process, it is important to study their mutagenic and genotoxic potential. In previous works in our laboratory, it was observed mutagenicity caused by the decoction when in high concentrations. Among the chemical compounds of this plant that could be able to induce mutation, the flavonoids were the only group that was referred to have either an oxidant or antioxidant potential. The flavonoids were isolated, purified and quantified by adsorptive column chromatography under silica gel, bacterial and in vitro genotoxic tests were realized to determine if the flavonoids were the responsible agents for this mutagenicity found. The tests realized with plasmidial DNA were indicative that the flavonoids are probably genotoxic, due to the presence of correlation between increase of the flavonoid concentration and in plasmidial DNA double strand breakage visualized in agarose gel, as well as they were capable to generated abasic sites shown by the in vitro treatment with exonuclease III. The same tests with plasmidial DNA in the presence of copper [10 µM] and of a Tris-HCl pH 7.5 [10 µM] buffer were realized with the isolated flavonoids to determine if there would be or not participation of reactive oxygen species (ROS). The transformation of plasmidial DNA in different bacterial strains proficient and deficient in DNA repair enzymes in the presence or not of a Tris-HCl buffer, suggests that the enzymes that repair oxidative lesions are necessary to repair the lesions generated by the flavonoids and that ROS are generated and are necessary to promote the lesions. Bacterial tests with Escherichia coli strains of the CC collection (deficient or not for DNA repair enzymes), showed that the flavonoids are able to increase the frequency of mutations, mainly in strains mutated in repair enzymes (MutM, MutY-glicosylases and double mutant), suggesting that these agents are responsible for the enhancement in the mutation rate. In order to determine the mutation spectrum caused by the flavonoids of the Brazilian pepper tree stem bark, plasmidial DNA previously treated with the flavonoids were transformed in bacterial strains deficient and proficient in the DNA repair enzymes, followed by a blue-white selection with X-gal, DNA amplification by PCR and sequencing the positive mutant clones. Analysis of the mutants obtained from strains CC104, CC104mutM, CC104mutY, CC104mutMmutY, BW9101, BW9109 indicated a predominance of some mutations like G:C to C:G that can be correlated with the origin of 8-oxoG, due to oxidative lesions caused by the flavonoids. So it can concluded that the flavonoid isolated or in fractions enriched on them are genotoxic and mutagenic, and their mutations are predominantly oxidative, mediated by ROS, and the lesions are recognized by the BER system. In this way it is proposed that the flavonoids can act in two different ways to generate the DNA lesion: 1. in a Fenton-like reaction, when the flavonoid are in the presence of metal ions and that together with the water generate ROS that promotes the DNA lesions; 2. in another way the lesions can be generated by the formation of ROS due to the internal chemical structure of the flavonoid molecule due to the quantity and location of hydroxyl groups, and so producing the DNA lesions, those lesions can be directly (suggested by the in vitro experiments) or indirectly done (supported by the experiments using the CC bacterial strains)

An electroanalytical application of 2-aminothiazole-modified silica gel after adsorption and separation of Hg(II) from heavy metals in aqueous solution

2-Aminothiazole covalently attached to a silica gel surface was prepared in order to obtain an adsorbent for Hg(II) ions having the following characteristics: good sorption capacity, chemical stability under conditions of use, and, especially, high selectivity. The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2-aminothiazole (SIAMT-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to + 0.6 V versus Ag/AgCl (0.02 mol L-1 KNO3; V = 20 mV s(-1)) show two peaks one at about 0.1 V and other at 0.205 V. The anodic wave peak at 0.205 V is well defined and does not change during the cycles and it was therefore further investigated for analytical purposes using differential pulse anodic stripping voltammetry in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n = 6) of 0.02 and 0.20 mg L-1 Hg(II) was 4.1 and 3.5% (relative standard deviation), respectively. The detection limit was estimated as 0.10 mu g L-1 mercury(II) by means of 3:1 current-to-noise ratio in connection with the optimization of the various parameters involved and using the highest-possible analyser sensitivity. (c) 2006 Elsevier Ltd. All rights reserved.

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l(-1) acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96 x 10(-4) to 1.07 x 10(-3) mol l(-1) with a detection limit of 8.0 x 10(-5) mol l(-1). The relative standard deviation was 1.2% for 1.96 x 10(-4) mol l(-1) isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method. (C) 2004 Elsevier B.V. All rights reserved.

Dietary copper absorption and excretion in three semi-terrestrial grapsoid crabs with different levels of terrestrial adaptation

Three species of phylogenetically related semi-terrestrial crabs (Superfamily Grapsoidea - Sesarma rectum, Goniopsis cruentata and Neohelice granulata (formerly: Chasmagnathus granulatus) with different degrees of terrestriality were studied to quantify the accumulation of copper (Cu) in hemolymph, gills, hepatopancreas and antennal gland, and its excretion through the faeces. These crabs were fed for 15 days practical diets containing 0 (A), 0.5 (B), 1.0 (C), and 1.5% (D) of added CuCl2 (corresponding to 0, 0.2, 0.5 and 0.7% of Cu2+, respectively). The amount of food ingested was directly proportional to the degree of terrestriality: S. rectum, the most terrestrial species, ate around 2-3 times more than the other crabs, whereas G. cruentata ate 1.5-2 times more than N. granulata, the least terrestrial. The amount of Cu excreted in the feces was proportional to Cu ingestion, and was 76.8% and 64.2% higher for Sesarma fed diet D compared to G. cruentata and N. granulata, respectively. Sesarma also displayed higher Cu concentration in the haemolymph, gills and antennal glands, but not in the hepatopancreas. A detoxifying mechanism followed by elimination was probably present at this last organ, preventing Cu accumulation. More terrestrial crabs, such as Sesarma, may accumulate more Cu in hemolymph and tissues, showing a correlation between metal accumulation and increased terrestriality. In this aspect, contaminated feed sources with Cu may have more impact in conservation of terrestrial crabs. (C) 2008 Elsevier B.V. All rights reserved.

Organic and inorganic sources of zinc, copper and selenium in diets for dairy cows: intake, blood metabolic profile, milk yield and composition

The present study was carried out with the objective of evaluating the effects of feeding dairy cows with organic or inorganic sources of zinc (Zn), copper (Cu) and selenium (Se) on blood concentrations of these minerals, blood metabolic profiles, nutrient intake and milk yield and composition. Nineteen Holstein cows were selected and randomly assigned to two groups for receiving organic (n = 9) or inorganic (n = 10) sources of Zn, Cu and Se from 60 days before the expected date of calving to 80 days of lactation. Samples of feed, orts and milk were collected for analysis. Body condition score (BCS) was determined and blood samples were collected for analysis of Zn, Cu and Se concentrations, as well as for metabolic profile. Supplying organic or inorganic sources of Zn, Cu, and Se did not affect dry matter and nutrient intake, blood metabolic profile, milk yield and composition, plasma concentration of these minerals, and BCS or change the BCS in cows from 60 days before the expected date of calving to 80 days of lactation. An effect of time was observed on all feed intake variables, plasma concentrations of Zn and Se, milk yield, milk protein content, BCS and change in BCS.

Electrochemical sensor for sulfite determination based on a nanostructured copper-salen film modified electrode

The electrochemical preparation described herein involved the electrocatalytic oxidation of sulfite on a platinum electrode modified with nanostructured copper salen (salen=N,N'-ethylenebis(salicylideneiminato)) polymer films. The complex was prepared and electropolymerized at a platinum electrode in a 0.1 mol L-1 solution of tetrabutylammonium perchlorate in acetonitrile by cyclic voltammetry between 0 and 1.4V vs. SCE. After cycling the modified electrode in a 0.50 mol L-1 KCI solution, the estimated surface concentration was found to be equal to 2.2 x 10(-9) Mol cm(-2). This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the copper(II)/copper(III) couple. The potential peaks of the modified electrode in the electrolyte solution (aqueous) containing the different anions increase with the decrease of the ionic radius, demonstrating that the counter-ions influence the voltammetric behavior of the sensor. The potential peak was found to be linearly dependent upon the ratio [ionic charge]/[ionic radius]. The oxidation of the sulfite anion was performed at the platinum electrode at +0.9V vs. SCE. However, a significant decrease in the overpotential (+0.45V) was obtained while using the sensor, which minimized the effect of oxidizable interferences. A plot of the anodic current vs. the sulfite concentration for chronoamperometry (potential fixed = +0.45V) at the sensor was linear in the 4.0 x 10(-6) to 6.9 x 10(-5) mol L-1 concentration range and the concentration limit was 1.2 x 10(-6) mol L-1. The reaction order with respect to sulfite was determined by the slope of the logarithm of the current vs. the logarithm of the sulfite concentration. (C) 2009 Elsevier Ltd. All rights reserved.

Determination of the chemical oxygen demand (COD) using a copper electrode: a clean alternative method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)